JPH04218569A - Composition for heat-stable molding - Google Patents

Abstract

PURPOSE: To obtain a composition which is prepared from a vinyl polymer, a specified aromatic polycarbonate, and a specified thermoplastic resin which are contained in a prescribed ratio, has no surface defect and good mechanical properties, and is useful for a molding, etc.

CONSTITUTION: A heat stable molding composition consisting of (A) 1-99 pts.wt. of a vinyl polymer such as polystyrene, (B) 0.5-15 pts.wt. of an aromatic polycarbonate of 10,000-300,000 weight average molecular weight which is based on a substituted dihydroxydiphenyl cycloalkane containing a bifunctional structural unit represented by the formula (R¹, R², are each H, a halogen, a 1-8C alkyl, a 5-6C cycloalkyl, etc.; (m) is 4-7; R³, R⁴ are each H, a 1-6C alkyl; X is carbon), and 0-75 pts.wt. of a polybutadiene grafted, for example, with styrene which is at least partially compatible with the component A and has a glass transition temperature of at least 10°C.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to thermoplastic molding compositions containing vinyl polymers and methods for their production.

0002

BACKGROUND OF THE INVENTION Many molding compositions made of vinyl polymers or copolymers with a good balance of properties at room and slightly elevated temperatures are difficult to find due to their insufficient thermal stability. Even after short exposure to relatively high temperatures, there is a noticeable deterioration of properties, which can also occur during processing. The damage includes surface defects such as bubbles and cracks, brown or black discoloration, and partial or complete loss of mechanical properties. These undesirable effects can be caused by radicals generated by cleavage of polymer chains.

[0003] Therefore, molding compositions of vinyl polymers must be stabilized by additives. In terms of preventing the degradation described above, many stabilizers,
In particular, compounds containing phenolic hydroxyl groups (eg R. Gaechter and H.
Mueller, Taschenbuch der Kunststoff-Additive
uch der Kunststof-Additive
e), Carl-Hansel-Verlag (Carl-Ha
nser-Verlag), Munich, 1979) and benzoin derivatives (German Patent Application No. 3).
434939) has already been proposed. One drawback of these stabilizers is their volatility. At high processing temperatures, stabilizers escape from the molding composition and form deposits on surface imperfections of the device or molded article during molding. Deterioration of mechanical properties such as toughness, heat resistance and chemical resistance has also been observed.

0004

SUMMARY OF THE INVENTION It has now been discovered that the addition of small amounts of polycarbonates based on substituted dihydroxydiphenylcycloalkanes improves the thermal stability of vinyl polymer molding compositions. This improvement in stability is not accompanied by a deterioration in the properties of the composition. Improved thermal stability is reflected in a lower tendency to discolor and lower molecular weight loss. Since the stabilizer is polymeric, the above-mentioned drawbacks do not occur.

The present invention comprises: A) 1-99 parts by weight of a vinyl polymer; B) 0.5-1 parts by weight of a vinyl polymer;
5 parts by weight, preferably 0.7-10 parts by weight and more preferably 1-7 parts by weight of certain aromatic polycarbonates based on substituted dihydroxydiphenylcycloalkanes, and C) Thermoplastic molding compositions containing 0-75 parts by weight of another thermoplastic resin.

[0006]

DESCRIPTION OF THE DRAWINGS The performance of the composition according to the invention is illustrated in the accompanying drawings in comparison with a control composition. The graph depicts torque versus residence time measured at 300°C for the specified compositions. 5r. p. m. The torque M that must be applied to maintain a constant rotational speed of is a measure of the melt viscosity of the product. The decrease in torque with respect to residence time is recorded. An increase in viscosity indicates an increase in molecular weight (crosslinking) and a decrease in viscosity indicates a decrease in molecular weight due to decomposition. The sharpness (slope) of the curve as the viscosity decreases is a measure of the molecular weight reduction of the product.

[0007]

DETAILED DESCRIPTION OF THE INVENTION Vinyl Polymers A Vinyl polymers in the concept of the present invention are homopolymers or copolymers of at least one vinyl monomer. Vinyl polymers according to the invention include rubber-free vinyl polymers (A.1), rubber-containing vinyl polymers (A.1), and rubber-containing vinyl polymers (A.1).
For example, graft polymers of vinyl monomers on rubber) (A
．． 2), mixtures of rubber-free and rubber-containing vinyl polymers are included.

Polymer A. 1 is resinous, thermoplastic, and rubber-free.

Preferred vinyl polymers A. 1 is styrene;
alpha-methylstyrene, ring-substituted styrenes, acrylates and methacrylates.

Preferred vinyl copolymers A. 1 is styrene, α-methylstyrene and/or ring-substituted styrene (A.1.1) on the one hand and acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride and/or N-substituted on the other hand It is a maleimide (A.1.2).

Thermoplastic copolymer A. A particularly preferred weight ratio of A.1 is 50-98% by weight of A.1. 1.1 and 50-2
Weight % A. It is 1.2.

Particularly preferred copolymers A. 1 is of styrene and/or alpha-methylstyrene with acrylonitrile and optionally methyl methacrylate.

Styrene/acrylonitrile copolymer A.
1 is known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. Copolymer A. 1 is preferably 15,000-20
Molecular weight Mw in the range of 0,000 (weight average, light diffusion,
or sedimentation).

Other particularly preferred copolymers according to the invention A.
No. 1 is a random copolymer of styrene and maleic anhydride which can be advantageously prepared with incomplete conversion from the corresponding monomers by continuous bulk or solution polymerization.

The percentage content of the two components of the styrene/maleic anhydride random copolymers suitable for the purposes of the invention can vary within wide limits. The preferred content of maleic anhydride is 5-25% by weight.

Instead of styrene, the polymer may contain ring-substituted styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted styrenes such as α-methylstyrene, It can also contain.

The molecular weight Mn (number average) of the styrene/maleic anhydride random copolymers suitable for the purposes of the invention can vary within a wide range. 60,000-2
A range of 00,000 is preferred. These products are
Preferably an intrinsic viscosity of 0.3-0.9 (measured in dimethylformamide at 25°C, manufactured by Hoffmann).
nn), Kromer, Kuhn
), Polymeranalytic
tik) I, Stuttgart, 1977, pp. 316 et seq.).

Vinyl polymers according to the invention A. 2 is thermoplastic and contains rubber. Preferred vinyl polymers A. 2 is a graft polymer. These graft polymers include, for example, essentially at least two of the following monomers: chloroprene, 1,3-butadiene, isoprene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and the number of carbon atoms in the alcohol component. is 1
-18 (meth)acrylates: Rubber obtained from -
Graft copolymers with elasticity, eg Methode
(Organischen Chemie)
, (Houben-Weyl)
, Vol. 14/1, George Chieme-Verlag, Stuttgart, 1961, pp. 393-406 and C. B
．． Bucknall, Toughened Plastics
, Applied Science Publishers, London, 1977. Preferred polymers A. 2 is partially crosslinked and has a gel content of 20% by weight or more, preferably 40% by weight or more, and more preferably 60% by weight or more.

Preferred graft polymers A. 2 includes A. 2
．． 25-95 parts by weight and preferably 20-
A. onto 70 parts by weight of a polymer having a glass transition temperature below -10°C. 2.1 5-95 and preferably 30-80 parts by weight of A. 2.1.1 50-95 parts by weight of styrene, α-methylstyrene, halogen-
or methyl-substituted styrenes, methyl methacrylate
, or mixtures of these compounds, and A. 2.
1.1 5-50 parts by weight of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, C1-4-alkyl- or phenyl-N-substituted maleimide, or compounds thereof
Graft polymers of copolymers of mixtures of substances are included.

Preferred graft polymers A. 2 are, for example, styrene- and/or acrylonitrile- and/or alkyl-(meth)acrylate-grafted polybutadienes, butadiene/styrene copolymers and acrylate rubbers, i.e. DE 1 694 173 (=U.S. Patent specification 3,564,0
77); alkyl-(meth)acrylate-, vinyl acetate-, acrylonitrile-, styrene- and/or alkylstyrene-grafted polybutadienes,
Butadiene/styrene or butadiene/acrylonitrile copolymers, for example DE 2 348
377 (=US Pat. No. 3,919,353).

Particularly preferred polymers A. 2 is, for example, German Patent Publication No. 2035 390 (= US Patent Specification 3
, 644, 574) or German Patent Publication 2 2
48 242 (= British patent specification 1,409,275)
ABS polymers of the type described therein.

Particularly preferred graft polymers A. 1 is β)
Grafting substrate A. Graft polymer A.2.2.
butadiene containing at least 50% by weight of butadiene units based on β, preferably 50-85% by weight and more preferably 60-80% by weight based on β α) Graft shell A. Graft polymer A as 2.1
．． 10-70% by weight based on 2, preferably 15-50
% by weight and more preferably 20-40% by weight of at least one acrylate or methacrylate or 10-70% by weight, preferably 15-50% by weight and more preferably 20-40% by weight. 10-50% by weight and preferably 20-35% by weight of acrylonitrile or acrylate or methacrylate and 50-90% by weight and preferably 65-80% by weight, based on the mixture.
obtained by grafting a mixture of styrene with % by weight, the gel content of the grafting substrate β is at least 7
0% by weight (measured in toluene), the degree of grafting G is 0.15-0.55, and the graft polymer A.
The average particle size d50 of No. 2 is 0.05-2 .mu.m and preferably 0.1-0.6 .mu.m.

Acrylates and methacrylates a
is acrylic acid or methacrylic acid and carbon number is 1-18
These are esters with monohydric alcohols. Particularly preferred are methyl, ethyl and propyl methacrylate, n-butyl acrylate, t-butyl acrylate and t-butyl methacrylate.

In addition to the butadiene units, the grafting substrate β contains up to 50% by weight, based on β, of other ethylenically unsaturated monomers, such as styrene, acrylonitrile, carbon atoms of 1-4 in the alcohol component. It may contain esters of acrylic or methacrylic acid (for example methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate), vinyl esters and/or vinyl ethers. A preferred grafting substrate β consists of pure polybutadiene.

In the concept of the present invention, the graft polymer A. The term 2 also includes products obtained by polymerizing graft monomers in the presence of a grafting substrate,
It is known that the graft monomers are not completely grafted onto the graft substrate during graft polymerization.

The degree of grafting G is the weight ratio of grafting monomers grafted onto the grafting substrate and is dimensionless.

The average particle size d50 is the diameter above and below which 50% by weight of the particles lie. It can be measured by ultracentrifugation measurements (W. Scholtan (
Scholtan), H. Lange, Colloid Zernal und Zernal Polymere (K
olroid Z. und Z. Polymere
), 250 (1972), 782-796).

Other particularly preferred polymers A. 2 is τ) Grafting substrate A. 2.2 as A. 20- based on 2
90% by weight of acrylate rubber with a glass transition temperature below -20°C, and δ) graft monomer A. 2.1
As, A. 10-80% by weight of at least one polymerizable ethylenically unsaturated monomer based on 2 (its homopolymers and copolymers formed in the absence of 1.
It is a graft polymer consisting of (having a glass temperature of 5° C. or higher).

Polymer A. The acrylate rubber τ of No. 2 is preferably a polymer of alkyl acrylates, which can optionally have up to 40% by weight, based on τ, of other polymerizable ethylenically unsaturated monomers. Suitable polymerizable acrylates include C1-8 alkyl esters, such as methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably halo-C1-8 alkyl esters, e.g. Included are chloroethyl acrylate as well as mixtures of these monomers.

Monomers containing one or more polymerizable double bonds can also be copolymerized for crosslinking. Examples of suitable crosslinking monomers include unsaturated monocarboxylic acids having 3-8 carbon atoms and unsaturated monohydric alcohols having 3-12 carbon atoms or containing 2-4 OH groups. Number of carbons is 2
-20 esters with saturated polyols such as ethylene glycol dimethacrylate, allyl methacrylate, polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate, polyfunctional vinyl compounds such as divinyl and trivinylbenzenes, and triallyl phosphate and diallyl phthalate.

Suitable crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least three ethylenically unsaturated groups.

Particularly preferred crosslinking monomers include the cyclic monomers triallylcyanurate, triallylisocyanurate, trivinyl cyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes. It is.

The crosslinking monomers are preferably used in an amount of 0.02-5% by weight and more preferably in an amount of 0.05-2% by weight, based on the grafting substrate τ. .

In the case of cyclic crosslinking monomers containing at least three ethylenically unsaturated groups, it is advantageous to limit their amount to less than 1% by weight of the grafting substrate. Suitable "other" polymerizable ethylenically unsaturated monomers which can optionally be used in addition to acrylates for the preparation of the grafting substrate τ are, for example, acrylonitrile, styrene, α
-Methylstyrene, acrylamide, vinyl-C1-
6-alkyl ether, methyl methacrylate, and butadiene. Acrylates suitable as grafting substrates are emulsion polymers with a gel content of at least 60% by weight.

Other suitable grafting substrates A. 2.2 is German Patent No. 3704 657, German Patent No. 37 04 6
55, a silicone rubber with graft-active sites of the type described in German Patent No. 36 31 540 and German Patent No. 36 31 539.

Graft substrate A. The gel content of 2.2 is
Measured in dimethylformamide at 25°C (
M. Hoffmann, H. Chromel (K
Romer), R. Kuhn, Polymeranalytik I and II, George Thiem-Verlag, Stuttgart, 1977).

Graft polymer A. 2 can be prepared by known methods such as bulk, suspension, emulsion or bulk-suspension polymerization.

Rubber-free polymer A. 1 and rubber-containing polymer A. Particularly preferred are mixtures of the two.

Polycarbonates B In the concept of the invention polycarbonates B are of the formula (I)

[0040]

[Case 2]

[Here, R1 and R2 are independently hydrogen, halogen, preferably chlorine or bromine, C1-
8 alkyl, C5-6 cycloalkyl, C6-10 aryl, preferably phenyl, and C7-12 aralkyl, preferably phenyl-C1-4-alkyl, more preferably benzyl, and m is 4-7 , preferably an integer of 4 or 5, R3 and R4 are selected individually for each X and independently of each other hydrogen or C1-6
alkyl, and X represents carbon, with the proviso that for at least one atom X, both R3 and R4 are alkyl]. 2,0
00 and preferably have a molecular weight Mw (weight average) in the range 10,000-300,000.

The starting compounds for polycarbonates B are:
Formula (II)

[0043]

[Chemical formula 3]

[where X, R1, R2, R3, R4 and m are as defined for formula (I)]
These are dihydroxydiphenylcycloalkanes corresponding to .

Preferably at 1-2 atoms X, and more preferably at only 1 atom X, both R3 and R4 are alkyl. A preferred alkyl group is methyl. The X atom in the α-position to the diphenyl-substituted C atom (C-1) is preferably not dialkyl-substituted, whereas the X atom in the β-position to C-1 is preferably dialkyl-substituted. There is.

Suitable dihydroxydiphenylcycloalkanes are those containing 5 and 6 ring atoms in the alicyclic group (m=4 or 5 in formula (II))
, for example diphenols corresponding to formulas (IIa)-(IIc)

[0047]

[C4]

[0048]

[C5]

[0049]

[C6]

1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (
Particular preference is given to formula (IIa)) in which R1 and R2=H.

The polycarbonates B can be prepared from diphenols according to DE 3 832 396.

Both single diphenols corresponding to formula (II) and several diphenols corresponding to formula (II) can be used, in the former case homopolycarbonates are prepared, and in the latter case homopolycarbonates are prepared; In this case, copolycarbonates are produced.

Furthermore, for the production of high molecular weight thermoplastic aromatic polycarbonates, it is possible to combine diphenols corresponding to formula (II) with other diphenols, for example

00
54]

[Chemical formula 7] HO-Z-OH
It can also be used in the form of a mixture with something corresponding to (III).

Other suitable diphenols corresponding to formula (III) are those in which Z is an aromatic group having 6 to 30 carbon atoms, which may contain one or more aromatic nuclei. , optionally substituted, and an aliphatic group or a group of the formula (
Other alicyclic groups or heteroatoms than those corresponding to II) can be contained as bridging members.

Examples of diphenols corresponding to formula (III) are hydroquinone, resorcinol, dihydroxydiphenyls, bis-(hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)-cycloalkanes. phenyl)-sulfides, bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfones, bis-(hydroxyphenyl)-
sulfoxides, α,α'-bis-(hydroxyphenyl)-diisopropylbenzenes and their ring-alkylated and ring-halogenated compounds.

These and other suitable diphenols are described, for example, in US Pat. No. 3,028,365, 2,
999,835, 3,148,172, 3,275,6
01, 2,991,273, 3,271,367, 3,
062,781, 2,970,131 and 2,999
, 846, German Patent Publication No. 1 570 703
, 2 063 050, 2 063 052, 2 21
1 0956, French Patent Specification 1 561518
Middle and H. A book entitled "Chemistry and Physics of Polycarbonates" by Schnell, Interscience Publishers, New York, 1.
964.

Other suitable diphenols include, for example, 4,
4'-dihydroxydiphenyl, 2,2-bis-(4-
hydroxyphenyl)-propane, 2,4-bis-(4
-hydroxyphenyl)-2-methylbutane, 1,1-
bis-(4-hydroxyphenyl)-cyclohexane,
α,α′-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl-
4-hydroxyphenyl)-propane, 2,2-bis-
(3-chloro-4-hydroxyphenyl)-propane,
Bis-(3,5-dimethyl-4-hydroxyphenyl)
-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, 2,4-
Bis-(3,5-dimethyl-4-hydroxyphenyl)
-2-methylbutane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, α,
α′-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-
(3,5-dichloro-4-hydroxyphenyl)-propane, and 2,2-bis-(3,5-dibromo-4-
hydroxyphenyl)-propane.

Particularly suitable diphenols corresponding to formula (III) are, for example, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxy phenyl)-methane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-
propane, and 1,1-bis-(4-hydroxyphenyl)-cyclohexane.

Particularly preferred is 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A).

The further diphenols can be used both individually and in mixtures with one another.

The molar ratio of diphenols corresponding to formula (II) to another optionally used diphenol corresponding to formula (III) is 100 mol % (II) to 0 mol % (III). ) to 20 mol% (II) to 80 mol% (
III) and preferably 100 mol% (
II) to 0 mol% (III) to 25 mol% (II)
) to 75 mol% of (III).

High molecular weight polycarbonates of diphenols corresponding to formula (II), optionally in combination with other diphenols, can be produced by methods known per se. The various diphenols can be combined with each other both randomly and in blocks.

Polycarbonates can also be branched by known methods. If branching is required,
It can be done in a known manner by adding a small amount, preferably 0.05-2.0 mol % (based on the diphenols used) of a trifunctional or more functional compound, in particular a compound with more than 3 phenolic hydroxyl groups. It is obtained by co-condensation of Branching agents containing three or more phenolic hydroxyl groups include phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hepten-2- , 4,6-dimethyl-2,4,6-tri-
(4-hydroxyphenyl)-heptane, 1,3,5-
Tri-(4-hydroxyphenyl)-benzene, 1,1
, 1-tri-(4-hydroxyphenyl)-benzene,
tri-(4-hydroxyphenyl)-phenylmethane,
2,2-bis-(4,4-bis-(4-hydroxyphenyl)-cyclohexyl)-propane, 2,4-bis-
(4-hydroxyphenylisopropyl)-phenol, 2,6-bis-(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl) )-propane, hexa-(4-(4-hydroxyphenylisopropyl)-phenyl)-ortho-terephthalic acid ester, tetra-(4-hydroxyphenyl)-methane, tetra-(4-(4-hydroxyphenylisopropyl))
-phenoxy)-methane, and 1,4-bis-((4
',4''-dihydroxytriphenyl)-methyl)-benzene is included.

Some examples of other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2 , 3-dihydroindole.

Monofunctional compounds can be used in customary concentrations as chain terminators for adjusting the molecular weight of polycarbonates B in a known manner. Suitable compounds are, for example, phenol, tertiary-butylphenols or other C1-7-alkyl-substituted phenols. Small amount of formula (IV)

[0067]

[Chemical formula 8]

Phenols corresponding to [wherein R is a branched C8 and/or C9 alkyl group] are
Particularly suitable for molecular weight adjustment. In the alkyl group R,
The percentage of CH3 protons is 47-89%, and the percentage of CH and CH2 protons is 53-11%. R is preferably o- and/or p to the OH group
- position, with 20% being a particularly preferred upper limit for the ortho component. Chain terminators are generally used in amounts of 0.5-10 mol% and preferably 1.5-8 mol%, based on the diphenols used.

Polycarbonates B can be produced by known methods, preferably by interfacial polycondensation (H.
Schnell, "Chemistry and Physics of Polycarbonates," Polymer Reviews, Vol. IX, pp. 33 et seq., Interscience Publishers, New York, 1964). In this method, the expression (
The diphenols corresponding to II) are dissolved in the alkaline aqueous phase. To prepare copolycarbonates with other diphenols, mixtures of diphenols corresponding to formula (II) and other diphenols, such as those corresponding to formula (III), are used. . To adjust the molecular weight, chain terminators can be added, for example those corresponding to formula (IV). The reaction is then carried out using phosgene, preferably in a polycarbonate-soluble inert organic phase, by an interfacial condensation method. The reaction temperature is in the range 0-40°C.

The optional branching agent (preferably 0.05-2 mol %) can be added initially to the alkaline aqueous phase together with the diphenols or phosgenated in solution in an organic solvent. It can also be added before.

In addition to the diphenols of formula (II) and any further diphenols (III), their mono-
It is also possible to use and/or bis-chlorocarbonate esters, which are added in solution in an organic solvent. The amount of chain terminator and branching agent used is determined by the molar amount of diphenolate units corresponding to formula (II) and any formula (III). If chlorocarbonate esters are used, the amount of phosgene can be reduced accordingly in known manner.

Suitable organic solvents for the chain terminator and optional branching agents and chlorocarbonates are, for example, methylene chloride, chlorobenzene, acetone, acetonitrile and mixtures of these solvents, especially methylene chloride and A mixture of chlorobenzenes. The chain terminator and branching agent used can optionally be dissolved in the same solvent.

The organic phase for interfacial polycondensation can be prepared, for example, from methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene.

For example, an aqueous NaOH solution can be used as the alkaline aqueous phase.

The preparation of polycarbonates B by interfacial polycondensation is catalyzed in a customary manner using catalysts such as tertiary amines, in particular tertiary aliphatic amines, such as tributylamine or triethylamine. be able to. The catalyst can be used in an amount of 0.05-10 mol%, based on the number of moles of diphenols used. The catalyst can also be added before the start of the phosgenation, during or after the phosgenation.

Polycarbonates B can also be produced by the known homogeneous phase process, the so-called "pyridine process", and by the known melt transesterification process, for example using diphenyl carbonate instead of phosgene.

Polycarbonates B preferably have a polycarbonate of at least 2,000 and more preferably 10,000-3
00,000 and most preferably 10,000
It has a molecular weight Mw (weight average, determined by gel chromatography after precalibration) in the range -80,000. They may be linear or branched and are homopolycarbonates or copolycarbonates based on diphenols corresponding to formula (II).

Particularly suitable polycarbonates B have the formula (
Structural units corresponding to I) in which m is 4 or 5, and more particularly formula (V)

[0079]

[Chemical formula 9]

[wherein R1 and R2 are as defined for formula (I), but are preferably hydrogen]
The unit is equivalent to .

The formula (
In addition to their high heat resistance, these polycarbonates based on diphenols corresponding to IIa) also exhibit high UV stability and unexpectedly good melt flow properties.

Thermoplastic resins C In addition to A and B, the molding material according to the invention can contain one or more thermoplastic resins C. Suitable thermoplastic resins are those that are at least partially compatible with A and have a glass transition temperature of 10°C or higher. By adding C, it is possible to improve, for example, the processability, stress cracking resistance or mechanical properties of the molding material. A suitable thermoplastic resin C is described in German Patent Application No. 2 407 6
47, 2 407 776 and 2 715 932,
U.S. Patent Specification 2,999,835, British Patent Specification 7
72,627 or German Patent Publication No. 3 334
Aromatic polycarbonates (C.2) of the type described in German Patent Application No. 872, DE 1 495 626
, 2 232877, 2 703 376, 3 000
610, 2 714 544, 2 940024 and 3 007934 (C.3), U.S. Pat.
264,536, British Patent Specification 1,264,900
and aromatic polysulfones (C.4) of the type described in European Patent Application Publication No. 38 028.

The molding compositions according to the invention contain other known additives for vinyl polymers, graft polymers and aromatic polycarbonates, such as stabilizers, pigments, mold release agents, flame retardants and antistatic agents. , in conventional amounts.

The molding composition according to the invention is prepared by mixing the components in a known manner and the resulting mixture being preferably heated at elevated temperatures in typical equipment such as an internal kneader, an extruder or a two-screw extruder. by melt-blending or melt-extruding at 200-350°C,
can be manufactured. The individual components can be mixed sequentially or simultaneously.

The invention therefore also relates to a process for producing the desired molding composition by mixing the components at elevated temperatures.

The molding compositions according to the invention can also be used for the production of molded articles of any kind, for example by injection molding. Examples of molded products include housing parts (e.g. household goods,
e.g. juice press, coffee maker, blender)
, cover panels for the building industry, or automotive parts. Furthermore, because they have very good electrical properties, they can also be used in electrical equipment, for example for multi-way connectors. Molded articles can also be produced by thermoforming from prefabricated sheets or films.

The invention therefore also relates to the use of the molding compositions described above for producing molded articles.

[0088]

Examples: Vinyl polymer A A1 Polystyrene A2 with a weight average molecular weight of 85,000 g/mol, produced by emulsion polymerization Styrene with an intrinsic viscosity of 0.55 dl/g (measured in dimethylformamide at 20° C.) /acrylonitrile copolymer (ratio of styrene to acrylonitrile
72:28) A3 Styrene/maleic anhydride copolymer containing 8% maleic anhydride with a number average molecular weight of 135,000 g/mol (Dylark 232, a product of Alco Polymers, Inc.) A4 Emulsion polymerization 55 parts by weight of granular crosslinked polybutadiene rubber (average particle size d50 = 0.4 μm) produced by
) of 45 parts by weight of styrene and acrylonitrile on top
Graft polymer A5 of copolymer in a ratio of 2:28 80 parts by weight of granular crosslinked polybutadiene rubber (average particle size d50 = 0.4 μm) produced by emulsion polymerization
) onto a graft polymer of 20 parts by weight of a copolymer of methyl methacrylate and n-butyl acrylate in a ratio of 90:10 Polycarbonate B Preparation: 1,436.4 g (6.3 mol) of bisphenol A [2,2 -bis-(4-hydroxy-phenyl)-
propane], 2,387.0 g (7.7 mol) of 1,1
-bis-(4-hydroxy-phenyl)-3,3,5-
Trimethylcyclohexane, 7,476.0 g (84 moles) of 45% NaOH and 33.7 liters of water were dissolved with stirring under an inert gas atmosphere. 36.9
A solution of g (0.392 mol) of phenol in 11 liters of methylene chloride and 13 liters of chlorobenzene was then added. 2,772 g (28 moles) of phosgene was then added to a well-stirred solution at pH 13-14/21-
Added at 25°C. Next, 14 ml of ethylpiperidine was added, followed by stirring for 45 minutes. The bisphenolate-free aqueous phase was separated and the organic phase, after acidification with phosphoric acid, was washed free of electrolyte and solvent with water. The polycarbonate had a relative solution viscosity of 1.30. The glass temperature of the polymer measured by DSC was 206°C.

Thermal Stability of Linear Polycarbonate Molding Compositions Based on Bisphenol A with a Relative Solution Viscosity of 1.26-1.28, Measured in Thermoplastic Resin C CH2Cl2 at a Concentration of 0.5 g/ml Test In a 1.3 liter internal kneader, the ingredients were
Melt, mix and homogenize at 260°C. The mixture was then granulated. Evaluation of the thermal stability of molding compositions is based on intrinsic color and modification upon exposure to heat.

a) The unique color granules upon heat exposure were placed in an open test tube placed in an adjustable heating block and stirred slowly (5 rpm) at 300° C. for 60 minutes. . At the start, 3
Color was visually evaluated after 0 and 60 minutes.

[0091]

[Table 1] Table 1: Evaluation of unique colors

Example
Ingredient classification
Unique color after the dwell time below
A1 A2 A3 A4 A5
B C 0 3
0 60 minutes
[weight%]

1 (comparison) 100 - -
− − − − White
Beige light brown 2
95 - - - - 5 -
White Light yellow Light yellow 3 (comparison) − 100 − −
− − − White Brown
Dark brown 4 -
95 - - - 5 -
White Beige Brown 5 (comparison)
− − 100 − − −
− White Beige Light brown 6 − − 95 −
- 5 - White
Beige Beige 7 (comparison) − −
- 100 - - -
white light brown black 8
− − − 95 −
5 - white beige
Light brown 9 (comparison) − − − −
100 - - White
Brown Dark brown 10 -
− − − 95 5 −
white pale yellow brown 1
1 (comparison) - 75 - 25 -
− − Light yellow beige
Dark brown 12-71-
24-5- pale yellow
Beige Brown 13 (comparison) −
16 - 24 - - 60
Light yellow beige brown 14
- 16 - 24 - 5
55 Light yellow Beige Light brown (comparative) = Comparative test The molding materials containing small amounts of polycarbonate B (Examples 2, 4, 6, 8, 10, 12 and 14) are similar to the comparative example ( Examples 1, 3, 5, 7, 9,
11 and 13) showed significantly more favorable performance.

b) For the measurement of denaturation during heat exposure, the outlet is a recorder (Rikadenki model WE21).
This was carried out using a rotational viscometer (Contraves Rheomat 115) connected to

To carry out the measurements, 8 g of granules, previously dried in vacuum, were placed in an open tube placed in an adjustable heating block and heated to 300° C. for 60 minutes. 5r. p. m. A cylindrical stirrer (length: 25 mm, diameter 8
The torque M that must exit through 0 mm) is a measure of the melt viscosity of the product. The recorder plotted the decrease in torque against dwell time. Viscosity increase is due to molecular weight (crosslinking)
The viscosity decrease indicates a decrease in molecular weight due to decomposition (J.I. Eguiazabal).
, Nazabal, Macromolecular
Chemistry (Makromol. Chem.), Macromolecular Symposium (Makromol.
Symp. ), 20/21 (1988), 255-2
67).

The material modification results (see Table 1) for selected examples are shown in FIGS. 1-5.

All of the stabilized molding materials, ie molding materials containing polycarbonate B, showed a notable reduction in viscosity drop.

The main features and aspects of the present invention are as follows.

1. A) 1-99 parts by weight of vinyl polymer;
B) 0.5-15 parts by weight,

[0098]

[Chemical formula 10]

[Here, R1 and R2 independently represent a member selected from the group consisting of hydrogen, halogen, C1-8 alkyl, C5-6 cycloalkyl, C6-10 aryl and C7-12 aralkyl. , m is 4
-7 integer, R3 and R4 are individually selected for each X and independently of each other hydrogen or C1-6
alkyl and X represents carbon, with the proviso that for at least one atom X both R3 and R4 are alkyl]. and C) 0-75 parts by weight of another thermoplastic at least partially compatible with said A and having a glass transition temperature of 10° C. or higher. A thermoplastic, heat-stable molding composition comprising a resin.

[0100]2. The molding composition of 1 above, wherein B is present in an amount of 0.7-10 parts by weight B.

[0101]3. The molding composition of 1 above, wherein B is present in an amount of 1-7 parts by weight B.

4. A is 50-98% by weight styrene;
alpha-methylstyrene, ring-substituted styrene, methyl methacrylate or mixtures thereof, and 50-2
The molding composition of 1 above, which is a thermoplastic rubber-free vinyl copolymer of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, N-substituted maleimide and mixtures thereof in weight percent.

5. The molding composition of 1 above, wherein A is a graft polymer of resin-forming vinyl monomer onto rubber.

6. The molding composition of 1 above, wherein A is a thermoplastic rubber-free vinyl copolymer and a graft polymer of a resin-forming vinyl monomer onto the rubber.

7. The graft polymer is applied onto 5-95 parts by weight of a rubber having a glass transition temperature of -10°C or less.
-95 parts by weight of styrene, α-methylstyrene, halogen- or alkyl-ring-substituted styrenes, C1-
8 alkyl methacrylates and C1-8 alkyl acrylates and 5-50 parts by weight of acrylonitrile, methacrylonitrile, C1-8 alkyl methacrylates, C1-
8 Alkyl acrylates, maleic anhydride, and C
5. The molding composition described in 5 above, which is obtained by graft polymerizing 5 to 95 parts of a graft monomer consisting of a 1-4 alkyl- or phenyl-N-substituted maleimide or a mixture of these compounds.

8. 5. The molding composition of 5 above, wherein the rubber is selected from the group consisting of diene rubber, acrylate rubber, silicone rubber and ethylene-propylene-diene rubber.

9. In addition, pigments, flow aids, mold cutting agents,
1. The molding composition of 1 above, which also contains at least one member from the group consisting of a flame retardant and an antistatic agent.

10. 1. The molding composition described in 1 above, wherein the other thermoplastic resin is at least one member selected from the group consisting of polyalkylene terephthalate other than the polycarbonate of B, aromatic polycarbonate, aromatic polyester carbonate, and aromatic polysulfone.

[Brief explanation of the drawing]

Results regarding compound degradation based on selected examples are shown in Figures 1-5.

FIG. 1 compares the performance of Examples 1 and 2.

FIG. 2 compares the performance of Examples 3 and 4.

FIG. 3 compares the performance of Examples 5 and 6.

FIG. 4 compares the performance of Examples 11 and 12.

FIG. 5 compares the performance of Examples 13 and 14.

Claims (2)

[Claims] Claim 1: A) 1-99 parts by weight of a vinyl polymer, B) 0.5-15 parts by weight, [wherein R1 and R2 are independently hydrogen, halogen, C1-8 alkyl, C5-6 cycloalkyl,
represents a member selected from the group consisting of C6-10 aryl and C7-12 aralkyl, m is an integer from 4-7, R3 and R4 are selected individually for each X,
and independently of each other represent hydrogen or C1-6 alkyl, and X represents carbon, with the proviso that for at least one atom X both R3 and R4 are alkyl]. an aromatic polycarbonate based on substituted dihydroxydiphenylcycloalkanes containing carbonate structural units, and C) 0-75 parts by weight of an aromatic polycarbonate at least partially compatible with said A and above 10°C. A thermoplastic, heat-stable molding composition comprising another thermoplastic resin having a glass transition temperature of . 2. A molding composition according to claim 1, wherein A is a graft polymer of a resin-forming vinyl monomer onto the rubber.